Tetrakisazo dyestuffs



:tetrak'is'azo dyestuffs Patented July 15, 1952 'TETRAKISAZO DYESTUFFS I "Werner Bossard, Bitterlin, Basel, Geigy A. G., Basel,

:No Drawing. Application November 20,

Riehen, near "Basel, and .Otto Switzerland, assignors to J. R.

Switzerland, 'a'Swiss firm rial No. 196,720. In Switzerland :November 25,

The present invention concerns the production of c'opperable'brown cellulose dyestufis'which are' distinguished "by their very good general properties.

' The group of copperable pclyazo dyestuffs which draw direct on to cellulose is very popular, because these dyestuffs are simple to 1150,8113 generally very fast to light and are also relatively cheap. They also gained in importance after the production of new types which, in addition to their other properties, are distinguished by excellent Wet fastness properties, as their coppered cellulose dyeings withstand-repeated soap washings without any important change of shade. A further important property which affects the fastness to wear and tear and therefore the .applicatien possibilitiesof such copperable dyetheiastness to perspiration. The new according. to the present vention now give coppered brown dyeings on cellulose fibres which are not onlyv distinguished .b very goodzfastness to lightwater and washing, but also, in :comparison with similar .known dyestuffs, are distinguished by improved fastness to acid and perspiration. They are, therefore, a great improvement on the "previously known similar dyestuffs.

The copperable tetrakisazo to this invention are obtained by combining 1 mol of a tetrazotised diamino compound of the general Formula I wherein'the right-hand N'I-Izgroup is attached to the adjacent benzene nucleus in'one of the positions 3 and 4, with 1 mol of-a disazo dyestuff' of "the general Formula II dyestuffs according '1 Claims.- (or-260 159) p-aminobenzoyl compound often have better properties than the corresponding dyestufis made up from the m-aminobenzoyl compound, and therefore are preferred.

Those diazonium compounds from aminonaphthalene sulphonic acids, particularly monosulphonic acids and preferably those from aminobjenzene sulphon'ic and carboxylic acids are employed for the introduction of the radical B.

. by heating in a caustic alkaline solution of the 'disazo dyestuff of the general Formula. II, the benzene ring of which can also contain 'iurther substituents usual in azo dyestuffs halogen, alky1 and alkoxy groups and, in contrast to the diamino compound of Formulal, can also contain groups suitable'for'the form'ationiqf a metal complex, in particularly the ortho hydroxy-carboxy configuration. The 3-aminobenzene-l-sulphonic acids and the 3-aminobenzene- .ll-carboxylic acids, of these for example metanilic acid, 6-chloroand 6-,methyl-3-aminobenzene sulphonic acids, G-hydroxy-aminobenzene carboxylic acid and 6-hydroxy-5-sulpho '3-aminobenzoic acid can be emphasised as particularly suitable compounds for the introduction of the radical R. The disazo dyestuff of the general- Formula II is obtained from the diazoniumcompounds of the above named aminonaphthalene and aminobenzene compounds by methods' known per se by coupling with a '2-a'c'ylamino *phenol, splitting off of the a'c'yl-radical by saponification, further diazotisation ofthe aminoazo dyestufi so obtained and coupling the diazoniumcompound with resorcinol.

In the form of their Water soluble alkali salts the dyestuffsaccording to this invention are dark powders whichdraw-verywell onto'cellulose fibres from a dyebath containing Glaubers salt under the usual conditions for direct dyestuffs. Coppering can take place in the-Ldyebath or in a freshbath with the usual copper salts, e. g. with copper sulphate or copper acetate in a neutral or weakly acid medium. If desired, copper compounds which are resistantto'alkali can be'used, .such as can be obtained for example by reacting'copper sulphate with sodium tartrate in a soda alkaline bath. p

Theffollo'wing examples illustrate various ways of performing the process without limiting it "in any way. Bart's are given as parts by weight and temperatures are in degrees centigrade, if

. EXAMPLE 1 15.13 parts of '1-amino-4-hydroxybenzene 5- "carboxylic, acid are diazotised in the usual Way with 6.9hparts of sodium nitrite and 16 parts of hydrochloric acid 30% in 300 parts of water. The diazo compound is then combined inthe presence of pyridine with a cold aqueous solution of 14.1 parts of l-iormylamino-2-hydroxybenzene, 15 parts of 30% caustic soda lye and 8A parts of sodium carbonate. On completion of the coupling, the formylamino group is saponified and at the same time the pyridine is removed. The dyestuff is then further diazotised by the addition of 7.6 parts of sodium nitrite and 20% by volume ofv common .salt and the rapid addition of hydrochloric acid .2, Congo red acid medium in -the cold. The diazonium compound so formed is such as v filtered off, "pasted with ice waterfand. coupled '69. parts of sodium nitrite andiarer-equpled with with a cold aqueous Solution of-ll parts of 1.3- 16 parts of 1'-acetylamino 2-hydroxybenzene in ydroxyb n n 3 parts of sodium carthe presence of 14.6 parts of 30% caustic soda lye bonate- On Completion f he C up i the and 25 parts of sodium carbonate. On complediSaZO dyestuff o me is pr ipitatedby the 5 tion ofthelcoupling, the dyestufi is saponified by ad it o ydrochloric acid until a Congolf heating with diluted caustic soda lye, it is then acid reaction is obtained, fil e ed .o ffi'anda ai -pr'ecipitatedco1d-with sulphuric acid and filtered dissolved in Water as sodium salt byithei dr pwi off.- The dyestuff i's then dissolved in water and addition of caustic soda lye. This solution-is 7 parts of 0% caustic Soda common pled with a tetrazo compound prod j 1 salt is added; and it is diazotised With 7.7 parts the usual a ner fr 1 -1 p s o 1- 0-' of scdium'nitrite, and 50 parts of hydrochloric benzoylamino)-4-aminobenzene, 11.6 parts of soacid (density L16) in the m The diazonium dium nitrite a d 4 P ts Of hydrochlorie compound is fi1tered ofi, and in a paste, is coupled acid in an acetic acid-medium and, after this with 11 parts f l 3 dihydroxybenzene in the te compound has disappeared, an aqueous 15 presence of partsofsodium carbonate The isolutionlof the sodium] salt Of 3.4v parts Of disazo. t is i t t t 125.1 3-methyl-5.-pyrazolone 1s;added. Thereafter, an hydrochloric .1* 1 t d;

aqilioflsisomtion parts of sodium bicarbo' solved in water and 20 parts of 30% caustic soda .-ne e mr of 1 add 9 ylye. The intermediate product is produced-by icpmplemn 0f the cuplmgl the l theaddition of this solution toth'eltetrazoicjomstufi o iithe formula? V and.-in;concentrated sulphuric acid. It dyes pound from 19.1 .parts of 1-(4-'-aminobenzoyl- ...-'ooii :1 amino)-4-aminobenzene'ina 'weak litmus-acid =-is..is.o1ated.and dried.

a :They tetrakisazo dyestufi is a dark powder solution. 8.4 parts of 3 methyl 5 pyrazolone are a i added in, a neutral aqueous solution and then which'dissolves with a brown colour 1n both water 72 partsof sodium bicarbonate in 144 pa bf water are added. On completion of the coupling,

natural or regenerated cellulose fibres in brown dyestufi is salted out hot filtered. and

. p undsllaccordingto one. of the usual methods, have eny goodfastness properties.'.' v I j I If 16.7:parts of 1-amino-3-methyl 4-hydroxy- ,benzene-5.-,.carboxylic acid, 23.3 parts of l -amino- 23.3 partsqof 1,-amino-2-hydroxy 3,-carboxybenzeneefi-sulphonic acid, 13.7 parts of. l ami'nobenderjieil-carboxylic' acid, .1 3;7; parts 101 l-amino- 1eamino-4-hydroxybenzene 5-carboxy1ic acid and 65 the above described method is followed} dyestufis i with similar properties are obtained. The "formula of the compound obtained when 13,7 partsof .1-aminobenzene 3-carboxylic. acid are ie ed I i scribed method is followed; dyestuffs with simishades which; after treatment with coppercom dried It corresponds -y formula.

The dyestufi, in the form of a dark powder.

dissolves in water and in concentrated sulphuric acid with a brown colour. It dyes cellulose fibres I in brown shades which, when treated with copper sulphate, have very good light, ashingQacid and 4 hydroxy-5 carboxybenzene 3 sulphomc acid, perspiration fastness properties; I If 20.75 parts of 1-amino-,2;chlorobenzene 5- sulphonic acid, 24.2 parts of 1-amino- .4-dichlorobenzene-6-su1phonic acid, 24.2 parts of benzene-d-carboxylic acid or, 18.85 parts. of 1 amino 4 hydroxy fi? chlorobenzene 5- carboxylic acid areu'sedinstead of 15.3 parts of parts of 1'amino'4'methylbenzenez' sulphonic acid, 18.7 parts of l-amino-Z-methylbenzene-5 -sulphonic acid, 21.7 parts of l-amino- 4 ethoxybenzene-'3 sulphonic acid, 223 "parts o'f l-aminonaphthalene-Fb, -5-' or '-6-sulp'honicacid are used instead of 20.75 parts of Famine-4'- chlorobenzene-3-sulphonic acid and'the above de- Co v V v v ooh N=N H J OH EXAMPLE 2 V i L $20 .75 parts of .1-amino-4 chlorobenzene-3-sullar properties are obtained. The formula df 'th e .phonicacid are diazotised in the usual way with compound obtained when18.7 parts of l-amino- 1 amino-3.6-dichlorobenzene-4-sulphonic acid, a

zgeosgesi I 4-methylbenzene-3-sulphonic acid are used is I EXAMPLE 3 The diazonium compound from. 13.7 parts of l-aminobenzene-3-carboxylic acid with 18.7 parts of 1--oxalylamino-2-hydroxybenzene in the presence of 29.2 parts of 30% caustic soda. lye-and 25 parts of sodium carbonate and the monoazo dyestuff so formed is saponified hot with diluted caustic soda lye.-- The dyestuff' is then further :diazotise'd cold with 716" parts of so= dium nitrite and 50 parts of hydrochloric acid (density L1G) in the presence of common salt. The diazonium compound is filtered off, and as a dispersion is coupled. with 11 parts. of 1.3-dihydroxybenzene and 40 parts of: sodium carbonate. The disazo dyestuff is precipitatedwith 100 parts of hydrochloric acid, filtered off and dissolved with water and 20 parts of 30% caustic soda lye. This solution is then added to the tetrazocompoundfrom 19.]. parts of 1- (3-aininobenzoylamino)-4-aminobenzene. After the intermediate product has formed in a weakly acetic acid solution, 8.4 parts of 3-.methyl-5-pyrazolone are added. in a neutral aqueous solution and is coupled within 30 minutes, 30 parts of SOIHI 1.5 parts of the dyestufi obtained according to Example 2 are dissolved in a dyebath in 3000 parts of water and-zvparts-of soda. 100 parts of cotton are entered at -50", the bath is heated to 90-95" sodium sulphate are added and dyeing is performed for minutes at this temperature. The dyed goods are then rinsed in cold water, and after-treated at 70 for 30 minutes in a fresh bath containing 2 parts of crystallised copper sulphate in 2000 parts of water and 2 parts of acetic acid. The goods are then rinsed and dried in the usual manner. The cotton is dyed in-brown shades with very good fastness properties. 3

Further dyestuffsproduced according to this invention and the processes described in Examples 1-3 of the following general formula are summarised in the following table, in which the diazo component introducing the radical R into the compound of the general Formula II is shown in columnl, and the diamino compound of the general Formula 115 shown in column 2:

H v I I N=NR Table Shade of pp r con ammg No Diazo component (B) NH: Diammo compound (I) dyeing on cellulose fibres L.-. l aniinobcnzene-3 sulphonic acid 1- (b 3 a min 0 b en z o y l a m ino)-4-amino- Brown.

6111261118. 2. l-amino-QA-dimcthylbenzene-G-sulphonic acid l-(l a min 0 1) en z o y 1 am i no )A-amino- Do.

' V QDZGIIQ. 3 l-arnino-4-hydroxybcnzene-3-carboxylic acid l-gg 'r a min 0 b e n z o y 1 a m ino )-4-amino- Do.

7 y I enzcne. 4..-; l-aminonaphthalen'el sulphonic acid do Do. 5..-. l-amin04-chlorobenzene-fi-sulphonic acid. do v Do. 6 l-aminobenzene-4-sulphonlc acid l-gi -amin obenzoylamino)-4-an1ino- Do.

enzene. 7..-. l-aminobcnzene-B-sulphonic acid do Do. 8. l-anuno-4-methylbenzcne-3-su1phonic acid l-Qg, a min 0 b on z o yl am ino )-4amino- Do. enzclle. 9. l-amino-2-chlorobenzene-fi-sulphonic acid .do Do.

finally 7.2 parts of sodium bicarbonate in 144 The formula of the dyestuff corresponding to item 7 of the foregoing table is as follows:

parts of water are added. The tetrakisazo dye- I stuff is filtered off hot and. dried. L

The dyestufi is a dark powder and dissolves in What we claim is:

1-.' A tetrakisazo dyestufi corresponding to the formula COJ wherelnxstands for the grouping V I OH 7 attached to the adjacent benzene nucleus in one of the positions 3 and 4, R representing a benzene Nikki ra'dical containing at least one water-solubilising V 5 group. p

N=N I I Q 2. A tetraklsazo dyestufi corresponding to the,

0H formula l. I I CH;'C' CHN=NONH'C OON=NOOH N='N-'R BN1 (L10 N/ a a ,e V

V. ;H y 1 r V H '7 t g V i V I Y 1 wherein R represents a benzene-radical contain 7 ing at least one water-solubilising' group. 7 g I r '3. A tetrakisazo dyestufi corresponding to the l v formula r 4. A tetrakisazo dyestuff formula 5. A tetrakisazo dyestuff corresponding to the formula corresponding to the 6. A tetrakisazo dyestuff corresponding to the formula Q t 0H CH;-fiCH-N=NONHC DON: 0H lTI=N-CH; N 430 v 1 r 1 V V N=N soln H V CH 7. A tetrakisazo dyestufi corresponding to the formula 0111-0 0 HN=N-NHC o -N=N 0 H N=N L 10 \N/ SOaH H OH WERNER BOSSARD. OTTO BITTERLIN.

REFERENCES CITED V 1 The following'references are of record in the file of this patent: V

UNI'I'EDSTATES PATENTS Number V Name Date 2,545,872 Bossard Mar. 20, 1951 

7. A TETRAKISAZO DYESTUFF CORRESPONDING TO THE FORMULA 